CN107250168B

CN107250168B - Polymerized oil and preparation method thereof

Info

Publication number: CN107250168B
Application number: CN201680011958.8A
Authority: CN
Inventors: T·库尔思; C·斯蒂弗梅尔; H·塔巴塔巴伊; S·尼文斯
Original assignee: Cargill Inc
Current assignee: Cargill Inc
Priority date: 2015-02-27
Filing date: 2016-02-26
Publication date: 2020-07-14
Anticipated expiration: 2036-02-26
Also published as: RU2017133092A; JP2018509540A; JP7371152B2; EP3262236A1; JP2024009999A; EP3262083A4; AU2016222570B2; CA2976949A1; CA2976949C; US20190119499A1; JP6857605B2; CA2976951A1; BR112017018131B1; US20180044528A1; WO2016138384A1; CN107250168A; JP7113096B2; US20180080180A1; CA2976950A1; US20190119498A1

Abstract

Described herein is a polymerized biorenewable, previously modified or functionalized oil comprising a polymer distribution having an oligomer content of about 2 wt.% to about 80 wt.%, a polydispersity index ranging from about 1.30 to about 2.20, and a sulfur content ranging from 0.001 wt.% to about 8 wt.%. Methods of making the polymerized oil and incorporating it into asphalt paving, roofing, and coating applications are also described.

Description

Polymerized oil and preparation method thereof

Cross Reference to Related Applications

This application claims the benefit of U.S. patent application No. 62/126,064 filed on 27/2/2015, which is incorporated by reference herein in its entirety.

Technical Field

The present disclosure relates to polymerized oils and methods for polymerizing oils and blending with asphalt to enhance the performance of neat asphalt (asphal) and/or pavement containing recycled and aged asphalt material.

Background

Recent technical challenges faced by the asphalt industry have created opportunities for introducing agricultural-based products for overall performance enhancement of asphalt. Such performance enhancements may include extending the Usable Temperature Interval (UTI) of the asphalt, rejuvenating aged asphalt, and compatibilizing elastomeric thermoplastic polymers in asphalt.

Summary of The Invention

Aspects described herein provide a polymeric oil comprising a polymer distribution having an oligomer content of about 2 wt% to about 80 wt%, a polydispersity index ranging from about 1.30 to about 2.20, and a sulfur content ranging from 0.001 wt% to about 8 wt%.

Other aspects described herein provide a method of polymerizing oil comprising heating a biorenewable, previously modified or functionalized oil to at least 100 ℃, adding a sulfur-containing compound to the heated oil, and reacting the sulfur-containing compound with the oil to produce a polymerized oil comprising a polymer distribution having an oligomer content of about 2 wt.% to about 80 wt.%, a polydispersity index ranging from about 1.30 to about 2.20, and a sulfur content ranging from 0.001 wt.% to about 8 wt.%.

Still other aspects described herein provide for the incorporation of the polymer oil in asphalt paving, roofing, and coating applications.

Description of the drawings

Fig. 1 and 2 show the complex modulus curves of bitumen as a function of decreasing loading frequency.

FIG. 3 shows a comparison of DSC specific heat curves.

Detailed description of the preferred embodiments

The "flash point" or "flash point temperature" is a measure of the lowest temperature at which a material initially flashes with a brief flame. It is measured using a Cleveland Open Cup (Cleveland Open Cup) according to the method of ASTM D-92 and reported in degrees Celsius (C.).

"oligomer" is defined as a polymer having a number average molecular weight (Mn) greater than 1000. The monomers constitute anything else and include Monoacylglycerides (MAG), Diacylglycerides (DAG), Triacylglycerides (TAG), and Free Fatty Acids (FFA).

"Performance grade" (PG) is defined as the temperature interval designed for a particular bitumen product. For example, a bitumen product designed to accommodate high temperatures of 64 ℃ and low temperatures of-22 ℃ has a PG of 64-22. Performance Grade standards are set by the American Association of State road and transport Officials (AASHTO) and the American Society for Testing Materials (ASTM).

The "polydispersity index" (also referred to as "molecular weight distribution") is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). Polydispersity data were collected using a gel permeation chromatography instrument equipped with a Waters 510 pump and a 410 differential refractometer. Samples were prepared at a concentration of approximately 2% in THF solvent. A flow rate of 1 ml/min and a temperature of 35 ℃ were used. The column consisted of a Phenogel 5 micron linear/mixed guard column at 50, 100, 1000 and 10000 angstroms and a 300x 7.8mm Phenogel 5 micron column (styrene-divinylbenzene copolymer). The molecular weight was determined using the following criteria:

the "usable temperature interval" (UTI) is defined as the interval between the highest and lowest temperatures designed for a particular bitumen product. For example, a bitumen product designed to accommodate a high temperature of 64 ℃ and a low temperature of-22 ℃ has a UTI of 86. For road-paving applications, seasonal and geographical extremes of temperature will dictate the UTI that must be designed for the asphalt product. UTI of bitumen is determined by a series of AASHTO and ASTM standard tests (also known as "performance grading" (PG) specifications) developed by the Strategic Highway Research Program (SHRP).

Asphalt and bitumen material

For the purposes of the present invention, asphalt binder and bitumen (bitumen) refer to the binder phase of an asphalt pavement. Bituminous material may refer to a blend of bituminous binder and other materials, such as aggregate or filler. The binder used in the present invention may be materials obtained from asphalt producing refineries, slagging, refinery vacuum tower bottoms, asphaltenes (pitch) and other residues of vacuum tower bottoms processing, as well as oxidized and aged asphalt from recycled asphalt materials such as Recycled Asphalt Pavement (RAP) and Recycled Asphalt Shingles (RAS).

Starting oil

Bio-renewable oils can be used as starting oil. Biorenewable oils may include oils isolated from plants, animals, and algae.

Examples of vegetable-based oils may include, but are not limited to, soybean oil, linseed oil, canola oil, rapeseed oil, castor oil, tall oil, cottonseed oil, sunflower oil, palm oil, peanut oil, safflower oil, corn distillers grain oil, lecithin (phospholipids), and combinations thereof, and crude streams.

Examples of animal-based oils can include, but are not limited to, animal fats (e.g., lard, tallow) and lecithin (phospholipids), and combinations and crude streams thereof.

Biorenewable oils may also include partially hydrogenated oils, oils with conjugated bonds, and thickened oils in which no heteroatoms are introduced, such as, but not limited to, diacylglycerides, monoacylglycerides, free fatty acids, alkyl esters of fatty acids (e.g., methyl, ethyl, propyl, and butyl esters), glycol and triol esters (e.g., ethylene glycol, propylene glycol, butylene glycol, trimethylolpropane), and mixtures thereof. An example of a biorenewable oil may be waste cooking oil or other used oil.

Previously modified or functionalized oils may also be used as starting materials. Examples of previously modified oils are those that have been previously vulcanized or polymerized by other polymerization techniques, such as maleic anhydride or acrylic acid modification, hydrogenation, dicyclopentadiene modification, conjugation by reaction with iodine, transesterification, or processing to change acid number, hydroxyl number, or other characteristics. Some examples of previously modified oils are polyol esters, such as polyglycerol esters or castor oil esters or polylactones. Such modified oils may be blended with unmodified vegetable-based or animal-based oils, fatty acids, glycerol, and/or lecithin. Examples of functionalized oils are those in which heteroatoms (oxygen, nitrogen, sulfur and phosphorus) have been introduced.

In a preferred aspect, the starting oil is recycled corn oil (a residual liquid typically produced from a manufacturing process for converting corn to ethanol) (also known as "corn stillage oil") or other low cost waste oil. In another preferred aspect, the starting oil comprises free fatty acids. One skilled in the art will recognize that if higher functionality is desired, vegetable-based oils with higher levels of unsaturation may be used.

Sulfur crosslinking of oils

In various aspects, polymerization of the biorenewable, previously modified or functionalized oil is achieved by crosslinking the glyceride moieties of the fatty acid chains and/or triglyceride molecules contained in the biorenewable, previously modified or functionalized oil using a sulfur-containing compound. The sulfur in the sulfur-containing compound is preferably in a reduced form. The polymerization process comprises the steps of: (a) heating a biorenewable, previously modified or functionalized oil, (b) adding a sulfur-containing compound to the heated oil, and (c) reacting the sulfur-containing compound with the oil to produce a polymerized oil having a desired polymer distribution (having an oligomer content of about 2 wt.% to about 80 wt.%), a polydispersity index (about 1.30 to about 2.20), and a sulfur content (between about 0.01 wt.% and about 8 wt.%).

In a first step, the biorenewable, previously modified or functionalized oil is heated to at least 100 ℃ in a vessel equipped with an agitator. In a more preferred aspect, the biorenewable, previously modified or functionalized oil (also collectively referred to herein as "oil") is heated to at least 115 ℃. In a preferred aspect, the sulfur-containing compound is gradually added to the heated biorenewable, previously modified or functionalized oil and may be added in solid or molten form, however, it is understood that the sulfur-containing compound may be added prior to or simultaneously with the oil. In a preferred aspect, the sulfur-containing compound may be elemental sulfur, but is not limited thereto. The reaction between sulfur and oil inherently increases the temperature of the oil-sulfur mixture, and in preferred aspects, the reaction is maintained at a temperature between about 130 ℃ and about 250 ℃, more preferably between about 130 ℃ and about 220 ℃, and even more preferably between about 160 ℃ and about 200 ℃ during the course of the reaction.

During the polymerization reaction between oil and sulfur, a gas-containing stream can be used continuouslyThe oil-sulfur mixture is injected. The gas-containing stream may be selected from the group consisting of nitrogen, air and other gases. The gas-containing stream may be advantageous in promoting the reaction and may also help reduce reaction-related odors (H) in the final product₂S and other sulfides). The use of air can be beneficial because it can cause oxidative polymerization of the oil in addition to the vulcanization process.

Optionally, a promoter may be used to increase the reaction rate. Examples of accelerators include, but are not limited to, zinc oxide, magnesium oxide, dithiocarbamates.

The reaction may continue and may be continuously monitored using Gel Permeation Chromatography (GPC) and/or viscosity until the desired degree of polymerization is achieved, as discussed below.

The robustness of the sulfur crosslinking reaction and the ability to use it for polymerizing lower cost feedstocks containing high free fatty acid content and residual moisture is an advantage of this polymerization process compared to other processes, thereby providing flexibility in starting material selection.

Polymerization characteristics

The reaction between the sulfur-containing compound and the biorenewable, previously modified or functionalized oil is driven until a polymer distribution is achieved having between about 2 wt.% and about 80 wt.% oligomers (20 wt.% to 98 wt.% monomer), and more preferably between about 15 wt.% and about 60 wt.% oligomers (40 wt.% to 85 wt.% monomer), and even more preferably between about 20 wt.% and about 60 wt.% oligomers (40 wt.% to 80 wt.% monomer). In an even more preferred aspect, the polymer distribution ranges from about 50% to about 75% by weight oligomers and from about 25% to about 50% by weight monomers.

The polydispersity index of the polymerized oil ranges from about 1.30 to about 2.20, and more preferably from about 1.50 to about 2.05.

The benefit of the reaction described herein is the low sulfur content in the resulting polymerized oil. In some aspects, the sulfur content comprises less than 8 wt% of the polymerized oil. In other aspects, the sulfur content comprises less than 6 weight percent of the polymerized oil. In yet other aspects, the sulfur content comprises less than 4 wt% of the polymerized oil. And in other aspects, the sulfur content comprises less than 2 weight percent of the polymerized oil. However, the sulfur content is at least 0.001 wt% of the polymerized oil.

The resulting polymerized oil has a flash point of at least about 100 ℃ and no more than about 400 ℃ as measured using the Cleveland open cup method. In some aspects, the flash point of the polymerized oil is between about 200 ℃ and about 350 ℃. In other aspects, the polymerized oil has a flash point between about 220 ℃ and about 300 ℃. In yet another aspect, the polymerized oil has a flash point between about 245 ℃ and about 275 ℃. The polymerized oils described herein can have a higher flash point than the starting oil, particularly when compared to other polymerization techniques.

The viscosity of the polymerized oil will vary depending on the type of starting stock, but will typically range from about 1cSt to about 100cSt at 100 ℃.

End use applications

In one aspect, the present invention provides a modified asphalt comprising a blend of 60 to 99.9 wt% of an asphalt binder and 0.1 to 40 wt% of a polymerized oil, wherein the polymerization of the oil is achieved by sulfur crosslinking as described above, and a method of making the same. The modified asphalt may be used in paving or roofing applications.

In another aspect, the present invention provides a modified asphalt comprising a blend of 60 to 99.9 wt% of an asphalt binder with 0.1 to 40 wt% of a polymeric oil and a method of making the same, wherein the polymeric oil is a blend of a polymeric oil as described above achieved by sulfur crosslinking with one or more of the aforementioned biorenewable, previously modified or functionalized oils (e.g., unmodified vegetable-based oils, animal-based oils, fatty acids, fatty acid methyl esters, gums or lecithins, and modified oils or gums or lecithins in other oils or fatty acids).

In addition to the polymeric oil, other components may be combined with the asphalt binder to produce modified asphalt, such as, but not limited to, thermoplastic elastomers and plastic polymers (styrene-butadiene-styrene, ethylene vinyl acetate, functionalized polyolefins, and the like), polyphosphoric acid, anti-stripping additives (amine-based, phosphate-based, and the like), warm mix additives, emulsifiers, and/or fibers. Typically, these components are added to the asphalt binder/polymer oil in amounts ranging from about 0.1% to about 10% by weight.

Modification of asphalt

The reduction in the quality of the bitumen drives the need for the addition of chemical modifiers to improve the quality of the bitumen product. Heavy mineral oils from petroleum refining are the most commonly used modifiers. These mineral oils extend the lower temperature limit of the bitumen product by "plasticizing" the binder, but this also tends to lower the upper temperature limit of the bitumen.

Flux Mineral oils (Mineral flux oil), petroleum-based crude oil distillates and re-refined Mineral oils have been tried for softening bitumen. Generally, the use of such materials results in a decrease in the high temperature modulus of the asphalt as compared to the low temperature, making the asphalt more prone to rutting at high temperatures. Such effects result in a reduction of the available temperature interval (UTI).

Flux mineral oils, petroleum-based crude oil distillates and re-refined mineral oils typically have a volatile fraction at road construction temperatures (e.g., 150 ℃ to 180 ℃), typically have a lower flash point than bitumen, and may be prone to higher performance losses due to oxidative aging.

The polymeric oils and blends described herein are not only viable alternatives to mineral oils, but have also been shown to extend the UTI of bitumen to a greater extent than other performance modifiers, thus providing considerable value to bitumen manufacturers. The increase in UTI observed with the polymeric oils described herein is a unique characteristic not seen in other asphalt softening additives, such as flux oil, fuel oil, or flush oil. Typically, a first grade improvement is achieved in the SHRP performance classification (PG) specification or penetration classification system used in many countries by about 2 to 3 wt% of polymerized oil by bitumen weight. For example, for a polymer oil addition of about 3 wt%, an increase in UTI of up to 4 ℃ can be seen, thus providing a broader range of PG modification so that the lower end temperature can be lower without sacrificing the higher upper end temperature.

Regeneration of aged bituminous material

Bitumen "ages" through a combination of mechanisms, primarily oxidation and volatilization. Aging increases asphalt modulus, reduces viscous dissipation and stress relaxation, and increases brittleness at lower performance temperatures. Thus, the asphalt becomes more susceptible to cracking and damage accumulation. The increasing use of recycled and reclaimed asphalt materials containing highly aged asphalt binders from sources such as Reclaimed Asphalt Pavement (RAP) and Recycled Asphalt Shingles (RAS) has created a need for "rejuvenating agents" capable of partially or fully restoring the rheological and fracture properties of aged asphalt. Aging of bitumen has also been demonstrated to increase colloidal instability and phase incompatibility by increasing the content of high molecular weight and highly polar insoluble "asphaltene" moieties that may be progressively associated. The use of the polymeric oils described herein is particularly useful for RAP and RAS applications. The polymerized oil described in this document acts as a compatibilizer for the asphalt fraction, particularly in aged and oxidized asphalt, such that a balanced and stable asphalt binder has restored performance and durability.

During plant production, bitumen is exposed to high temperatures (typically between 150 ℃ and 190 ℃) and to air, during which significant oxidation and volatilization of the lighter fraction can occur, resulting in an increase in modulus and a decrease in viscosity behavior. The aging process was simulated using a rolling film oven (ASTM D2872) during which a rolling film of asphalt was subjected to a jet of hot air at about 163 ℃ for about 85 minutes. Rheological Properties before and after aging procedure were measured using a dynamic shear rheometer following ASTM D7175, using | G before and after aging^*Ratio of | sin, wherein G^*Is the complex modulus and is the phase angle. The greater the ratio of (G/sin) after aging to (G/sin) before aging, the greater the influence of oxidative aging and volatilization on the asphalt being tested.

Using this procedure, it was shown that the bitumen treated with the polymeric oil or blends thereof described in this invention has a lower ratio, thus indicating a lower tendency to change rheological properties due to oxidative aging and volatilization.

Thus, the polymerized oils described herein have been shown to be able to rejuvenate aged asphalt binders and alter the rheological properties of less aged asphalt binders. Thus, high levels of aged recycled asphalt material can be incorporated into roadways and other applications using small doses of polymerized oil, resulting in significant economic savings by reducing the use of new resources and possibly reducing the environmental impact of the roadway surface.

Compatibilization of elastomeric thermoplastic polymers in asphalt

Asphalt is typically modified with thermoplastic elastomers and plastic polymers, such as styrene-butadiene-styrene (SBS), to increase high temperature modulus and elasticity, to increase resistance to heavy traffic loads, and to toughen the asphalt matrix to resist damage build up due to repetitive loads. Such polymers are typically used in dosages of 3 to 7 wt% in bitumen and are high shear blended into the bitumen at temperatures in excess of 180 ℃ and allowed to "set" at similar temperatures during which the polymer swells by adsorbing the lighter fraction in the bitumen until a continuous volume phase is achieved in the bitumen.

The volume phase of the fully cured polymer will be affected by the degree of compatibility of the polymer in the bitumen and the fineness of the dispersed particles, thus increasing the specific surface area and enhancing the swelling potential by increasing the interfacial surface between bitumen and polymer.

When the polymeric oils described in this document are added and blended into asphalt prior to incorporation into the polymer or curing stage, the oils have been shown to be capable of further compatibilizing the elastomeric polymer in the asphalt. This would be particularly effective for asphalt binders that are not very compatible with elastomeric polymers. In addition, the oil may contribute to the lighter fraction of the swelling of the polymer during curing.

Warm mix additive and asphalt

In recent years, more and more pavement sections have been produced using additives commonly referred to as "warm mix additives" to produce "warm mix" asphalt pavements. . Warm mix pavements can be produced and compacted at lower production temperatures, require less compaction force to achieve the target mix density, and therefore can maintain the characteristics required for compaction at lower temperatures, thereby enabling an increase in the maximum transport distance of the asphalt mix from the plant to the job site.

Different mechanisms by which warm mix additives provide benefits include increasing aggregate lubricity during compaction of the asphalt mixture, reducing binder viscosity at production temperatures, and making the coating and wetting of the aggregate better. Thus, when added to a bituminous mixture, a wide variety of chemicals and additives may exhibit one or more characteristics attributable to warm-mix additives.

The polymeric oils described herein may be used as warm-mix additives and/or compaction aids to achieve many of the benefits expected from warm-mix additives, including minimal reduction in production and construction temperatures by increasing aggregate lubricity and aggregate wettability. In such applications, the additive is preferably used in an amount ranging between about 0.1% and 2% by weight of the bitumen.

Examples

The following examples are presented to illustrate the present invention and to assist one of ordinary skill in making and using the same. The examples are not intended in any way to otherwise limit the scope of the invention.

Experimental methods

A charge of precipitated sulphur (mass range between 6.5 and 56.5 grams) was added to a 1 litre round bottom flask containing 650 grams of vegetable oil. The reactor was then heated to the target reaction temperature using a heating mantle, taking care not to exceed the target temperature by more than 5 ℃. The reaction mixture was agitated using an electric stirrer with a stirring shaft and blades. The reaction was continuously sparged with nitrogen at 2-12 standard cubic feet per hour (SCFH). A condenser and receiving flask were used to collect any distillate.

It should be noted that when sulfur is incorporated into the oil, the reaction will produce a foam of about 110 ℃ to 115 ℃. The reaction was monitored using GPC to measure oligomer content and distribution, and viscosity was measured using ASTM D445 at 40 ℃. The reaction is considered complete when the desired oligomer content is achieved. The reactor was then cooled to 60 ℃.

Example 1: asphalt modified with polymerized palm oil #1

A modified asphalt binder comprising:

97.0 wt% neat (i.e., unmodified) asphalt binder, rated as a standard grade of PG64-22 (and a "true" grade of PG 64.88-24.7) Note: the true grade represents the exact temperature at which the asphalt meets the control specification value, which always meets and exceeds the corresponding standard grade (i.e., the true high temperature grade will always be higher than the standard high temperature grade, and the true low temperature grade will always be lower than the standard low temperature grade).

3.0% by weight of sulphurised refined palm oil, which is reacted with 3% by weight of elemental sulphur at 160 ℃ for 5 hours under nitrogen sparge. This gave a modifier with:

omicron 31.8% oligomer

O has a viscosity of 17.2cSt at 100 ℃

A polydispersity index (PDI) of about 1.30

After annealing the binder at 150 ℃ for 1 hour, the modifier was blended into the asphalt. The performance rating test was performed according to AASHTO M320. The modification produced a low temperature grade improvement of 4.8 ℃, changing the neat binder grade of PG64-22 to PG 58-28. The net change in high and low performance levels increases the usable temperature interval by 0.8 ℃. The details are shown in table 1.

TABLE 1

¹UTI: available temperature interval as the difference between the high temperature performance rating and the low temperature performance rating as determined using AASHTO M320.

²O-DSR: high temperature performance rating of unaged ("virgin") asphalt binder as measured using a Dynamic Shear Rheometer (DSR) following ASTM D7175 and AASHTO M320.

³R-DSR: rolling thin film oven aged (RTFO, following ASTM D2872) asphalt binder high temperature performance grade as measured using Dynamic Shear Rheometer (DSR) following ASTM D7175 and AASHTO M320.

⁴S-BBR: such as following ASTM D6648 and AASHTO M320 using a bending Beam rheometer versus a Rolling film oven (ASTM D2872) and pressure aging vessel (ASTM D2872)D6521) Both adjusted asphalt binders measured low temperature performance ratings controlled by the creep stiffness parameter ("S").

⁵m-BBR: low temperature performance rating controlled by creep rate parameter ("M" value) as measured using a bending beam rheometer on asphalt binders conditioned using both a rolling film oven (ASTM D2872) and a pressure aged container (ASTM D6521) following ASTM D6648 and AASHTO M320.

Example 2: asphalt modified with polymerized palm oil #2

A modified asphalt binder comprising:

97.0% by weight of a pure asphalt binder, which is classified as PG64-22 (true PG 64.88-24.7)

3.0% by weight of sulphurised refined palm oil, which was reacted with 4% by weight of elemental sulphur at 160 ℃ for 20.5 hours under nitrogen sparge. This gave a modifier with:

omicron 56.18% oligomer

O has a viscosity of 25.0cSt at 100 ℃

O about 1.50 PDI

After annealing the binder at 150 ℃ for 1 hour, the modifier was blended into the asphalt. The performance rating test was performed according to AASHTO M320. The modification produced a low temperature grade improvement of 5.9 ℃, changing the neat binder grade of PG64-22 to PG 58-28. The net change in high and low performance levels increases the usable temperature interval by 1.5 ℃. The details are shown in table 2.

TABLE 2

Example 3: recovery of corn oil #1 modified asphalt by vulcanization

A modified asphalt binder comprising:

3.0 weight percent sulfurized Recovered Corn Oil (RCO) reacted with 1.5 weight percent elemental sulfur at 160 ℃ for 7 hours under nitrogen sparge. This gave a modifier with:

omicron 16.0% oligomer

O about 1.50 PDI

After annealing the binder at 150 ℃ for 1 hour, the modifier was blended into the asphalt. The performance rating test was performed according to AASHTO M320. The modification produced a low temperature grade improvement of 6.0 ℃, changing the neat binder grade of PG64-22 to PG 58-28. The net change in high and low performance levels increases the usable temperature interval by 0.4 ℃. The details are shown in table 3.

TABLE 3

Example 4: recovery of corn oil #2 modified asphalt by vulcanization

A modified asphalt binder comprising:

3.0 weight percent sulfurized Recovered Corn Oil (RCO) reacted with 6.0 weight percent elemental sulfur at 160 ℃ for 6 hours under nitrogen sparge. This gave a modifier with:

omicron 50.3% oligomer

Viscosity at 40 ℃ of 270cSt

A PDI of about 2.19

After annealing the binder at 150 ℃ for 1 hour, the modifier was blended into the asphalt. The performance rating test was performed according to AASHTO M320. The modification produced a low temperature grade improvement of 4.4 ℃, changing the neat binder grade of PG64-22 to PG 58-28. The net change in high and low performance levels increases the usable temperature interval by 0.7 ℃. The details are shown in table 4.

TABLE 4

Example 5: leaching modified with sulfurized refined sunflower oil blend #1Green leaf of Chinese cabbage

A modified asphalt binder comprising:

3.0% by weight of a blend having:

o 14.5 wt% of a sulfidised refined sunflower oil, which was reacted with 7.0 wt% of elemental sulphur at 160 ℃ for 19 hours under nitrogen sparge. This gave a modifier with 70.8% oligomer

Omicron 85.5 weight percent of refined sunflower oil

The blend of sulfurized and unmodified oils has an oligomer content of 11.9%, a viscosity of 55cSt at 40 ℃, and a PDI of about 1.64.

After annealing the binder at 150 ℃ for 1 hour, the modifier was blended into the asphalt. The performance rating test was performed according to AASHTO M320. The modification produced a low temperature grade improvement of 5.3 ℃, changing the neat binder grade of PG64-22 to PG 58-28. The net change in high and low performance levels produces a complete improvement in low temperature levels without a change in the available temperature interval. Details are shown in table 5.

TABLE 5

Example 6: asphalt modified with vulcanized refined sunflower oil blend #2

A modified asphalt binder comprising:

3.0% by weight of a blend having:

53.9% by weight of sulphur refined sunflower oil, which was reacted with 7.0% by weight of elemental sulphur at 160 ℃ for 19 hours under nitrogen sparge. This gave a modifier with 70.8% oligomer

46.1% by weight of refined sunflower oil

The blend of sulfurized and unmodified oil has an oligomer content of 42.76%, a viscosity of 177Cst at 40 ℃, and a PDI of approximately 3.16.

After annealing the binder at 150 ℃ for 1 hour, the modifier was blended into the asphalt. The modification produced a low temperature grade improvement of 4.8 ℃, changing the neat binder grade of PG64-22 to PG 58-28. The performance rating test was performed according to AASHTO M320. The net change in high and low performance levels increases the usable temperature interval by 0.1 deg.c. Details are shown in table 6.

TABLE 6

Example 7: asphalt modified with vulcanized refined sunflower oil blend #3

A modified asphalt binder comprising:

3.0% by weight of a blend having:

63.4% by weight of a sulfided refined sunflower oil, which was reacted with 7.0% by weight of elemental sulphur at 160 ℃ for 19 hours under nitrogen sparge. This gave a modifier with 70.8% oligomer

Omicron 36.6 weight percent of refined sunflower oil

The blend of sulfurized and unmodified oils has an oligomer content of 48.3%, a viscosity of 254Cst at 40 ℃, and a PDI of approximately 3.55.

After annealing the binder at 150 ℃ for 1 hour, the modifier was blended into the asphalt. The performance rating test was performed according to AASHTO M320. The modification produced a low temperature grade improvement of 5 ℃ changing the neat binder grade of PG64-22 to PG 58-28. The net change in high and low performance levels increases the usable temperature interval by 0.8 ℃. Details are shown in table 7.

TABLE 7

Example 8: asphalt modified with blend of refined sunflower oil and palm oil #1

A modified asphalt binder comprising:

3.0% by weight of a blend having:

O 84.5% by weight of palm oil

The blend of sulphur oil and palm oil has an oligomer content of about 11.9%

O about 1.77 PDI

After annealing the binder at 150 ℃ for 1 hour, the modifier was blended into the asphalt. The performance rating test was performed according to AASHTO M320. The modification produced a low temperature grade improvement of 5 ℃ changing the neat binder grade of PG64-22 to PG 58-28. The net change in high and low performance levels is a slight decrease of 0.2 c in the usable temperature interval. The details are shown in table 8.

TABLE 8

Example 9: asphalt modified with a blend of sulfurized refined sunflower oil and palm oil #2

A modified asphalt binder comprising:

3.0% by weight of a blend having:

59.0% by weight of sulphur refined sunflower oil, which was reacted with 7.0% by weight of elemental sulphur at 160 ℃ for 19 hours under nitrogen sparge. This gave a modifier with 70.8% oligomer

41.0% by weight of palm oil

The blend of sulfurized oil and palm oil has an oligomer content of about 43% and a PDI of about 2.37

After annealing the binder at 150 ℃ for 1 hour, the modifier was blended into the asphalt. The performance rating test was performed according to AASHTO M320. The modification produced a low temperature grade improvement of 4.2 ℃, changing the neat binder grade of PG64-22 to PG 58-28. The net change in high and low performance levels is a slight decrease of 0.1 c in the usable temperature interval. Details are shown in table 9.

TABLE 9

Example 10: asphalt modified with sulfurized soy acid oil (also known as "acidified soapstock")

A modified asphalt binder comprising:

3.0 wt.% sulfurized refined soy acid oil reacted with 5.0 wt.% elemental sulfur at 160 ℃ for 8 hours under nitrogen sparge. This gave a modifier with 28.14% oligomer, a viscosity of 167cSt at 40 ℃, and a PDI of about 2.36. After annealing the binder at 150 ℃ for 1 hour, the modifier was blended into the asphalt. The performance rating test was performed according to AASHTO M320. The modification produced a low temperature grade improvement of 3.3 ℃, changing the neat binder grade of PG64-22 to PG 58-28. The net change in high and low performance levels reduces the usable temperature interval by 1.5 ℃. This example highlights the potential undesirable effect of free fatty acid content on modifier performance, as it is significantly less effective in improving low temperature performance ratings than the reduction caused in high temperature ratings. Details are shown in table 10.

Watch 10

Example 11: with styreneAsphalt modified with butadiene styrene and sulfurized recovered corn oil #1 as solubilizer

A modified asphalt binder comprising:

92.41% by weight of a pure asphalt binder, which is classified as PG64-22 (true PG 64.88-24.7)

5.5% by weight of a linear Styrene Butadiene Styrene (SBS)

0.09% by weight of elemental sulfur (used as SBS crosslinker in asphalt binders)

2.0% by weight of sulfurized Recovered Corn Oil (RCO) as described in example # 3.

Blending procedure:

1. after annealing the binder at 150 ℃ for 1 hour, the modifier was blended into the asphalt. The modified binder was heated to about 193 ℃ for polymer modification.

2. The RPM in the high shear mixer was set to 1000 while SBS was added (over 1 minute). Immediately after the addition of the polymer, the RPM was briefly ramped up to 3000RPM for approximately 10 minutes to ensure complete breakdown of the SBS pellets, after which the shear level was reduced to 1000 RPM.

3. The polymer blending was continued at 1000rpm for a total of 2 hours.

4. The temperature was lowered to about 182 ℃ at 150rpm, at which point the sulfur crosslinking agent was added.

5. Blending was continued at 182 ℃ and 150rpm for 2 hours.

6. The polymeric binder was placed in an oven at 150 ℃ for about 12-15 hours (overnight) to allow the polymer to fully swell.

The performance rating test was performed according to AASHTO M320. The multi-stress creep and recovery tests were performed on unaged binders at 76 ℃ and on RTFO residues at 64 ℃ according to AASHTO T350. The results show that for the binder containing the modifier, the average percent recovery of the binder increases despite the decrease in modulus, indicating the effect of the modifier as a compatibilizer for SBS, resulting in the same quality of elastomeric polymer with better distribution and therefore a more efficient elastic network than the binder without the modifier. Details are shown in table 11.

TABLE 11

Example 12: regeneration of highly aged asphalt Binder Using the oil of example #3

The example shown in FIG. 1 shows the complex modulus (G) of the asphalt as a function of decreasing loading frequency^*) Curves, measured using a Dynamic Shear Rheometer (DSR) following ASTM D7175. Measurements were made on samples of asphalt binder (PG64-22) used in example #3 after laboratory aging to three levels:

aging level 1: oxidative ageing was carried out in a rolling film oven at 163 ℃ for 85 minutes (following astm d 2872).

Aging level 2: the samples after ageing level 1 were further aged by oxidative ageing at 100 ℃ for 20 hours under an air pressure of 2.1MPa using a pressure ageing vessel (following ASTM D6521). The PAV aging for 20 hours accelerates the simulated aging that typically occurs during the life of an asphalt pavement according to performance grading specifications.

Aging level 3: the samples after aging levels 1 and 2 were further aged by oxidative aging using a Pressure Aging Vessel (PAV) for an additional 20 hours to achieve a total of 40 hours of PAV aging, which represents the level of aging of the binder from severely aged pavement.

Fig. 1 shows that additional aging from level 1 to level 2, and from level 2 to level 3, results in a significant increase in complex modulus across the decreasing spectrum.

The aged level 3 asphalt binder was "rejuvenated" by heating the binder to 150 ℃ for 1 hour, and blending in 5 wt% of the total binder of example #3 oil. The curves corresponding to the rejuvenating binder in fig. 1 show that the rejuvenation significantly reduces the G of aged bitumen over the entire spectral range^*Resulting in a binder having significantly less rheological characteristics than an aged asphalt binder.

Example 13: use the factExample #4 oil regeneration of highly aged asphalt Binder

The example shown in FIG. 1 shows the complex modulus (G) of the asphalt as a function of decreasing loading frequency^*) Curves, measured using a Dynamic Shear Rheometer (DSR) following ASTM D7175. Measurements were made on samples of the asphalt binder used in example #3(PG64-22) after laboratory aging to three levels as described in example 12, and as previously described, showed that additional aging resulted in a significant increase in complex modulus across the decreasing spectrum.

The aged level 3 asphalt binder was "rejuvenated" by heating the binder to 150 ℃ for 1 hour, and blending in 5 wt% of the total binder of example #4 oil. The curves corresponding to the rejuvenating binder in fig. 2 show that the rejuvenation significantly reduces the G of aged bitumen over the entire spectral range^*Resulting in a binder having less rheological properties than an aged asphalt binder.

Example 14: effect of sulfurized oils on glass transition

The low temperature properties of asphalt have been shown to be significantly affected by the glass transition temperature of asphalt, which will occur in the performance temperature range often experienced in winter (about-5 ℃ to-40 ℃). In addition, the rate of physical hardening of bitumen has also been shown to be closely related to the glass transition of bitumen, with the highest rate occurring at the Tg. Therefore, it is desirable to have a low glass transition temperature to reduce the likelihood that the asphalt will reach its glass transition during its service life. Aging is known to increase the glass transition temperature of bitumen, and therefore a desirable attribute of an effective rejuvenating agent is to reduce the glass transition of the aged bitumen once incorporated.

The first measurement was made of PG64-22 asphalt binder after significant laboratory aging. Laboratory aging included oxidative aging in a rolling film oven (ASTM D2872) at 163 ℃ for 85 minutes followed by oxidative aging at 100 ℃ for 40 hours at 2.1MPa air pressure using a pressure aging vessel (following ASTM D6521), which represents the level of aging of the binder from severely aged pavement. The sample is labeled "aged bitumen" in figure 1.

The second sample, labeled "aged bitumen + polymer oil", comprises:

95% by weight of the pure binder PG58-28 described above

5% by weight of sulfurized corn oil (RCO) reacted with 1.5% by weight of elemental sulfur at 160 ℃ for 7 hours under nitrogen sparge. This gave a modifier with 16.0% oligomers and a PDI of about 1.50.

Thermal analysis of the binder before and after rejuvenation using polymerized oil showed that the modifier shifted the Tg of the aged bitumen significantly to lower temperatures, as shown in table 12. A comparison of DSC specific heat curves is shown in FIG. 3.

TABLE 12

Description of the materials	Glass transition temperature (. degree. C.)
		Aged asphalt	-17
Aged asphalt + polymerized oil	-27

Claims

1. A polymeric oil comprising a biorenewable, previously modified or functionalized oil crosslinked with a sulfur-containing compound or elemental sulfur, comprising:

(a) a polymer distribution having an oligomer content of 2 to 80 wt%, wherein the oligomer is a polymer having a number average molecular weight of greater than 1000;

(b) a polydispersity index ranging from 1.30 to 2.20; and

(c) a sulfur content ranging from 0.001 wt% to 8 wt%.

2. The polymerized oil of claim 1, wherein the polymer distribution has an oligomer content of 15 to 60 wt.%.

3. The polymerized oil of claim 1, wherein the polydispersity index ranges from 1.50 to 2.05.

4. The polymerized oil of claim 1, wherein the sulfur content is less than 6 wt.%.

5. The polymerized oil of claim 1, wherein the sulfur content is less than 4 wt.%.

6. The polymerized oil of claim 1, wherein the sulfur content is less than 2 wt.%.

7. The polymerized oil of claim 1, having a flash point in the range of from 100 ℃ to 400 ℃.

8. The polymerized oil of claim 1, having a flash point in the range of from 200 ℃ to 350 ℃.

9. The polymerized oil of claim 1, having a flash point in the range of 245 ℃ to 275 ℃.

10. The polymerized oil of claim 1, wherein the polymerized oil is derived from a starting oil stock selected from the group consisting of: palm oil, sunflower oil, corn oil, soybean oil, canola oil, rapeseed oil, linseed oil, tung oil, castor oil, tall oil, cottonseed oil, peanut oil, safflower oil, corn distillers grain oil, and combinations thereof and crude streams.

11. The polymerized oil of claim 1, wherein the polymerized oil is derived from a starting stock comprising alkyl esters.

12. The polymerized oil of claim 11, wherein the polymerized oil is derived from a starting oil stock selected from the group consisting of: methyl, ethyl, propyl and butyl esters and combinations thereof.

13. The polymerized oil of claim 1, wherein the polymerized oil is derived from a starting stock that has been previously modified.

14. The polymerized oil of claim 1, wherein the polymerized oil is derived from a starting oil stock selected from the group consisting of: triacylglycerides, diacylglycerides, monoacylglycerides, and combinations thereof.

15. The polymerized oil of claim 1, wherein the polymerized oil is derived from a starting oil material comprising a phospholipid.

16. The polymerized oil of claim 1, wherein the polymerized oil is derived from a starting stock comprising animal fat.

17. The polymerized oil of claim 1, wherein the polymerized oil is derived from a starting oil stock comprising recovered corn oil.

18. The polymerized oil of claim 1, wherein the polymerized oil is derived from a starting stock comprising free fatty acids.

19. The polymerized oil of claim 1, wherein the polymerized oil is derived from a starting oil comprising a partially hydrogenated oil.

20. A modified asphalt comprising the polymer oil of claim 1.

21. A modified asphalt for use in a composition for paving roads comprising the polymer oil of claim 1.

22. A modified asphalt for use in a composition for roofing materials comprising the polymeric oil of claim 1.

23. A rejuvenating agent for use in asphalt, comprising the polymeric oil of claim 1.

24. A performance grade improver for use in asphalt comprising the polymeric oil of claim 1.

25. A compatibilizer for use in asphalt comprising the polymeric oil of claim 1.

26. The polymeric oil of claim 1, further comprising at least one from the group consisting of thermoplastic elastomeric polymers, thermoplastic plastomer polymers, polyphosphoric acid, anti-peel additives, warm mix additives, and fibers.

27. A method of polymerizing a biorenewable, previously modified or functionalized oil, comprising:

(a) heating a biorenewable, previously modified or functionalized oil to at least 100 ℃;

(b) adding a sulfur-containing compound or elemental sulfur to the heated oil; and

(c) reacting the sulfur-containing compound or elemental sulfur with the oil to produce a polymerized oil crosslinked with the sulfur-containing compound or elemental sulfur, comprising:

i. a polymer distribution having an oligomer content of 2 to 80 wt%, wherein the oligomer is a polymer having a number average molecular weight of greater than 1000;

a polydispersity index in the range of 1.30 to 2.20; and

a sulfur content ranging from 0.001 wt.% to 8 wt.%.

28. The method of claim 27, further comprising step (d) of passing a gas-containing stream through the reaction mixture during step (c).

29. The method of claim 28, wherein the gas-containing stream is selected from the group consisting of nitrogen, air, and an inert gas.

30. The method of claim 27, wherein the oil is heated to at least 115 ℃ in step (a).

31. The method of claim 27, wherein the sulfur-containing compound or elemental sulfur is added in solid form.

32. The method of claim 27, wherein the sulfur-containing compound or elemental sulfur is added in molten form.

33. The method of claim 27, wherein the sulfur-containing compound is a reduced form of sulfur.

34. The method of claim 27, further comprising adding an accelerator after step (b).

35. The method of claim 27, wherein the oligomer content ranges from 15 wt.% to 60 wt.%.

36. The method of claim 27, wherein the polydispersity index ranges from 1.50 to 2.05.

37. The method of claim 27, wherein the sulfur content is less than 6 wt.%.

38. The method of claim 27, wherein the sulfur content is less than 4 wt.%.

39. The method of claim 27, wherein the sulfur content is less than 2 wt.%.

40. The method of claim 27, wherein the polymerized oil has a flash point ranging from 100 ℃ to 400 ℃.

41. The method of claim 27, wherein the polymerized oil has a flash point ranging from 200 ℃ to 350 ℃.

42. The method of claim 27, wherein the polymerized oil has a flash point ranging from 245 ℃ to 275 ℃.

43. A modified asphalt comprising the polymer oil prepared according to claim 27.

44. A modified asphalt for use in a composition for paving comprising the polymer oil prepared according to claim 27.

45. A modified asphalt for use in a composition for roofing materials comprising the polymeric oil prepared according to claim 27.

46. A rejuvenating agent for use in asphalt, comprising the polymerized oil prepared according to claim 27.

47. A performance grade improver for use in asphalt comprising the polymeric oil prepared according to claim 27.

48. A compatibilizer and swelling agent for use in asphalt comprising the polymeric oil prepared according to claim 27.

49. A warm mix additive for use in asphalt comprising the polymerized oil prepared according to claim 27.

50. A modified asphalt, comprising:

(a)60 to 99.9 wt% of an asphalt binder; and

(b)0.1 to 40% by weight of a polymeric oil crosslinked with a sulfur-containing compound or elemental sulfur, comprising

a polydispersity index in the range of 1.30 to 2.20; and

a sulfur content of less than 8 wt.%.

51. The modified asphalt of claim 50, wherein the asphalt binder is used in paving applications.

52. The modified asphalt of claim 50, where the asphalt binder is used in roofing applications.

53. The modified asphalt of claim 50, where the asphalt binder is used in coating applications.

54. The modified asphalt of claim 50, further comprising at least one from the group consisting of thermoplastic elastomeric polymers, thermoplastic plastomer polymers, polyphosphoric acid, anti-strip additives, warm mix additives, emulsifiers, and fibers.

55. A modified asphalt, comprising:

(a)60 to 99.9 wt% of an asphalt binder; and

(b)0.1 to 40 weight percent of a blend of a polymeric oil and an unmodified biorenewable oil, a previously modified or functionalized oil, wherein the polymeric oil is crosslinked with a sulfur-containing compound or elemental sulfur, and the polymeric oil has

a polydispersity index in the range of 1.30 to 2.20; and

a sulfur content of less than 8 wt.%.

56. The modified asphalt of claim 55, further comprising at least one from the group consisting of thermoplastic elastomeric polymers, thermoplastic plastomer polymers, polyphosphoric acid, anti-strip additives, warm mix additives, emulsifiers, and fibers.

57. A method of incorporating a polymerized oil in asphalt applications, comprising:

(a) obtaining a polymerized oil crosslinked with a sulfur-containing compound or elemental sulfur, comprising:

a polydispersity index in the range of 1.30 to 2.20; and

a sulfur content of less than 8 wt.%; and

(b) adding the polymerized oil to an asphalt binder to obtain a modified asphalt; wherein the amount of the polymerized oil ranges from 0.1 to 40 wt% of the modified asphalt.

58. A method of incorporating a polymerized oil in asphalt applications, comprising:

a polydispersity index in the range of 1.30 to 2.20; and

a sulfur content of less than 8 wt.%; and

(b) adding the polymerized oil to an aggregate to be used in an asphalt pavement, thereby obtaining a modified asphalt; wherein the amount of the polymerized oil ranges from 0.1 to 40 wt% of the modified asphalt.

59. A method of incorporating a polymerized oil in asphalt applications, comprising:

a polydispersity index in the range of 1.30 to 2.20; and

a sulfur content of less than 8 wt.%; and

(b) adding the polymerized oil to an aggregate to be used in asphalt roofing, thereby obtaining a modified asphalt; wherein the amount of the polymerized oil ranges from 0.1 to 40 wt% of the modified asphalt.

60. A method of incorporating a polymerized oil in asphalt applications, comprising:

a polydispersity index in the range of 1.30 to 2.20; and

a sulfur content of less than 8 wt.%; and

(b) adding the polymerized oil to an aggregate to be used in an asphalt coating prior to applying the asphalt to obtain a modified asphalt once the aggregate is blended with the asphalt; wherein the amount of the polymerized oil ranges from 0.1 wt% to 40 wt% of the modified asphalt.

61. A method of incorporating a polymerized oil in asphalt applications, comprising:

a polydispersity index in the range of 1.30 to 2.20; and

a sulfur content of less than 8 wt.%; and

(b) adding the polymerized oil to treat recycled asphalt pavement mill-base (RAP) to be reused in asphalt pavement, thereby obtaining modified asphalt; wherein the amount of the polymerized oil ranges from 0.1 wt% to 40 wt% of the modified and rejuvenated asphalt.

62. The method of claim 61, further comprising blending the treated recycled asphalt pavement mill stock with bitumen.

63. A method of incorporating a polymerized oil in asphalt applications, comprising:

a polydispersity index in the range of 1.30 to 2.20; and

a sulfur content of less than 8 wt.%; and

(b) adding the polymerized oil to an emulsion comprising water, an emulsifier, bitumen, and a thermoplastic polymer.

64. The method of claim 63, further comprising treating recycled asphalt pavement mill-base (RAP) with said emulsion having said polymerized oil, wherein said treated RAP is reused in asphalt pavement or applied to the surface of existing asphalt pavement to obtain modified and reclaimed asphalt; wherein the amount of the polymerized oil ranges from 0.1 to 40 wt% of the modified and rejuvenated asphalt.

65. A method of incorporating a polymerized oil in asphalt applications, comprising:

a polydispersity index in the range of 1.30 to 2.20; and

a sulfur content of less than 8 wt.%; and

(b) adding the polymerized oil into asphalt to be used as a warm-mix additive and/or a compaction aid, so as to obtain modified asphalt; wherein the warm-mix additive is in the range of 0.1 wt% to 2 wt% of the modified asphalt.